Lithium ion battery comprising nanomaterials

ABSTRACT

A lithium ion battery includes a cathode ( 10 ) having a plurality of nanoparticles of lithium doped transition metal alloy oxides represented by the formula Li x Co y Ni z O 2 , an anode ( 20 ) having at least one carbon nanotube array ( 22 ), an electrolyte, and a membrane ( 30 ) separating the anode from the cathode. The carbon nanotube array includes a plurality of multi-walled carbon nanotubes ( 23 ). Preferably, an average diameter of an outermost wall of the multi-walled carbon nanotubes is in the range from 10 to 100 nanometers, and a pitch between adjacent multi-walled carbon nanotubes is in the range from 20 to 500 nanometers. In the carbon nanotube array, the lithium ions are able to intercalate not only inside the multi-walled carbon nanotubes, but also in the interstices between adjacent multi-walled carbon nanotubes. Thus a density of intercalation of the carbon nanotube array is significantly higher than that of graphite.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to lithium ion batteries, and more particularly to lithium ion batteries comprising nanomaterials.

[0003] 2. Description of Prior Art

[0004] Lithium ion batteries are popularly used because of their high capacity and environmentally friendly features. These batteries are becoming of increasing importance for a wide variety of uses, ranging from portable electronics to power supply devices for spacecraft. There is an ongoing need for advanced lithium ion batteries with higher capacity.

[0005] A conventional lithium ion battery comprises an anode, a cathode, an electrolyte, and a membrane. The membrane separates the anode from the cathode. The membrane is porous, allowing ions to pass therethrough while blocking electrons from passing therethrough. The membrane can be made from polyethylene, polypropylene or polystyrene. The cathode is generally made of lithium (Li) doped transition metal oxides such as LiMO₂ (M=cobalt, nickel or manganese) that function as electron donors. Atoms of the electron donor undergo an oxidation reaction to form ions of lithium, and free electrons. These ions travel through the membrane and are absorbed by the anode by a reduction reaction, and the free electrons travel through an electrical circuit to provide electrical current. The anode is generally made of materials comprising carbon, such as graphite or carbon fibers. The carbon materials can readily intercalate lithium ions. Since the number of electrons “given away” by each atom of the electron donor is known, by measuring the number of electrons transferred through the electrical circuit, the number of ions transferred can be determined. This quantity is related to the specific capacity of the battery, which can be expressed in milliampere-hours per gram of the material. For example, the maximum specific (reversible) capacity of graphite to accept lithium ions is reported to be approximately 372 mAh/g, characterized as (LiC₆) in an article by J. R. Dahn et al. entitled “Mechanisms for Lithium Insertion in Carbonaceous Materials” (Science, Volume 270, Oct. 27, 1995).

[0006] Other carbonaceous materials are used as electrodes in advanced lithium ion batteries. Carbon nanotubes are considered to be promising candidates for electrode materials. These nanotubes can be visualized as “rolled-up” sheets of carbon hexagons, providing a superior intercalation medium for lithium ion batteries. The intercalation capacity of single-walled carbon nanotubes has been reported by Jijun Zhao et al. in an article entitled “First-Principles Study of Li-Intercalated Carbon Nanotube Ropes” (Physical Review Letters, Vol. 85, P1706˜1709, 2000). Results of the study show that, energetically, the insides of carbon nanotubes are as favorable as interstitial sites between carbon nanotubes for intercalation of lithium ions, and that the intercalation potential of single-walled carbon nanotubes is similar to that of graphite. Further, the density of the intercalated lithium ions in single-walled carbon nanotubes is higher than that in graphite, being up to about Li_(0.5)C.

[0007] U.S. Pat. No. 6,280,697 discloses a lithium ion battery employing single-walled carbon nanotubes as an electrode, and a method for making the electrode. The method comprises the following steps: preparing single-walled carbon nanotubes by laser ablation; washing and purifying the single-walled carbon nanotubes to obtain a purified material containing over 80% by volume of single-walled carbon nanotubes; placing the purified carbon nanotubes in a suitable solvent to form a solution; immersing a suitable substrate in the solution to deposit a film having the single-walled carbon nanotubes therein on the substrate; driving off the solvent to leave the film of the single-walled carbon nanotubes covering at least an upper surface of the substrate and to promote adhesion of the film to the substrate. The substrate with the single-walled carbon nanotubes deposited thereon can then be used as an electrode of a lithium ion battery. However, the laser ablation method does not provide for satisfactorily control of the diameter, length or direction of growth of the single-walled carbon nanotubes formed, and the yield of this method is relatively low. Moreover, excess amorphous carbon nanoparticles and metal catalysts are produced along with the single-walled carbon nanotubes, thus necessitating complicated purification processes. In summary, industrial production of single-walled carbon nanotubes using this method is problematic, and the capacity of the lithium ion battery employing the single-walled carbon nanotubes as electrodes formed by this method is limited.

SUMMARY OF THE INVENTION

[0008] Accordingly, an object of the present invention is to provide a lithium ion battery comprising nanomaterials which has a high charge capacity.

[0009] Another object of the present invention is to provide a lithium ion battery comprising nanomaterials which is suitable for industrial-scale production.

[0010] In order to achieve the objects set out above, a lithium ion battery in accordance with a preferred embodiment of the present invention comprises a cathode comprising a plurality of nanoparticles of lithium doped transition metal alloy oxides represented by the formula Li_(x)Co_(y)Ni_(z)O₂, an anode comprising at least one carbon nanotube array, an electrolyte, and a membrane separating the anode from the cathode. The nanoparticles of Li_(x)Co_(y)Ni_(z)O₂ have an average diameter in the range from 10 to 100 nanometers. The carbon nanotube array is formed by chemical vapor deposition, and comprises a plurality of multi-walled carbon nanotubes substantially parallel to each other. Diameters, densities and lengths of the multi-walled carbon nanotubes can be controlled. Preferably, an average diameter of outermost walls of the multi-walled carbon nanotubes is in the range from 10 to 100 nanometers, and a pitch between any two adjacent multi-walled carbon nanotubes is in the range from 20 to 500 nanometers. Spaces inside the multi-walled carbon nanotubes are generally as favorable for intercalation of lithium ions as interstices between adjacent multi-walled carbon nanotubes, in terms of energy required. The intercalation potential of each multi-walled carbon nanotube is comparable to that of graphite. In the carbon nanotube array, the lithium ions are able to intercalate not only inside the multi-walled carbon nanotubes, but also in the interstices between adjacent multi-walled carbon nanotubes. Thus a density of intercalation of the carbon nanotube array is significantly higher than that of graphite.

[0011] Other objects, advantages and novel features of the present invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings, in which:

BRIEF DESCRIPTION OF THE DRAWINGS

[0012]FIG. 1 is a schematic, side elevation view of a lithium ion battery in accordance with a preferred embodiment of the present invention;

[0013]FIG. 2 is a schematic, enlarged view of an exemplary anode of the battery of FIG. 1;

[0014]FIG. 3 is schematic, enlarged view of another exemplary anode of the battery of FIG. 1;

[0015]FIG. 4 is a schematic, enlarged end view of one multi-walled carbon nanotube of the anode of FIGS. 2 or 3; and

[0016]FIG. 5 is a schematic view of a carbon nanotube array formed on a substrate in accordance with the present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION

[0017] Referring to FIG. 1, a lithium ion battery in accordance with a preferred embodiment of the present invention comprises a cathode 10, an anode 20, an electrolyte (not labeled), and a membrane 30 separating the cathode 10 from the anode 20.

[0018] The cathode 10 can be made of lithium doped transition metal oxides formed on a conductive substrate (not shown). In the preferred embodiment, the cathode comprises a plurality of nanoparticles of lithium doped transitional metal alloy oxides represented by the formula Li_(x)Co_(y)Ni_(z)O₂. An average diameter of the nanoparticles is in the range from 10 to 100 nanometers. The nanoparticles of Li_(x)Co_(y)Ni_(z)O₂ can be prepared by sintering or another suitable method. A large surface area and high chemical activity of Li_(x)Co_(y)Ni_(z)O₂ nanoparticles is favorable for intercalation of lithium ions therein.

[0019] The electrolyte comprises a solvent and solute. The solvent is preferably propylene carbonate, ethylene carbonate or dimethyl carbonate. The solute is preferably lithium hexafluorophosphate (LiPF₆), lithium tetrafluorobarate (LiBF₄), or lithium perchlorate (LiClO₄). The membrane 30 deposited in the electrolyte separates the cathode 10 from the anode 20. The membrane 30 is porous, allowing ions to pass therethrough while blocking electrons from passing therethrough. Generally, the membrane 30 is made of polyethylene, polypropylene or polystyrene.

[0020] Referring to FIGS. 2-3, the anode 20 comprises a conductive substrate 21 and at least one carbon nanotube array 22 formed thereon. Depending on a shape of the lithium ion battery, the conductive substrate 21 may be, for example, rectangular (FIG. 2) or circular (FIG. 3). The carbon nanotube array 22 is formed by transplanting pre-prepared carbon nanotubes onto the conductive substrate 21. The carbon nanotube array 22 comprises a plurality of multi-walled carbon nanotubes 23 substantially parallel to each other and perpendicular to the conductive substrate 21. Each multi-walled carbon nanotube 23 comprises a plurality of hollow coaxial tubes having different diameters (see FIG. 4). An average diameter of an outermost wall of the multi-walled carbon nanotubes 23 is in the range from 10 to 100 nanometers. A pitch (not labeled) between any two adjacent multi-walled carbon nanotubes 23 is in the range from 20 to 500 nanometers. The coaxial tubes of each multi-walled carbon nanotube 23 can be visualized as “rolled-up” sheets of carbon hexagons. Each sheet has a structure similar to that of graphite. Spaces inside the multi-walled carbon nanotubes 23 are generally as favorable for intercalation of lithium ions as interstices between adjacent multi-walled carbon nanotubes 23, in terms of energy required. The intercalation potential of each multi-walled carbon nanotube 23 is comparable to that of graphite. In the carbon nanotube array 22, the lithium ions are able to intercalate not only inside the multi-walled carbon nanotubes 23, but also in the interstices between adjacent multi-walled carbon nanotubes 23. Thus a density of intercalation of the carbon nanotube array 22 is significantly higher than that of graphite.

[0021] Referring to FIG. 5, the carbon nanotube array 22 is preferably formed on a substrate 24 by using chemical vapor deposition. The substrate 24 can be silicon wafer. Generally, the method comprises the following steps: depositing a catalyst layer (not shown) on the substrate 24; annealing the substrate 24 with the catalyst layer thereon to form catalyst particles having nano-sized diameters (not shown); heating a reaction chamber up to a suitable temperature and introducing a carbon source gas to grow the carbon nanotube array 22 on the catalyst particles. Carbon nanotubes formed by chemical vapor deposition are mostly multi-walled carbon nanotubes 23. The multi-walled carbon nanotubes 23 are substantially parallel to each other and substantially perpendicular to the substrate 24. Diameters and densities of the catalyst particles, which can be controlled by annealing, determine diameters and densities of the multi-walled carbon nanotubes 23. A height of the carbon nanotube array 22 is controlled by a time of growing of the multi-walled carbon nanotubes 23. Generally, the height of the carbon nanotube array 22 can be up to several tens of micrometers or more.

[0022] It is understood that the invention may be embodied in other forms without departing from the spirit thereof. Thus, the present examples and embodiments are to be considered in all respects as illustrative and not restrictive, and the invention is not to be limited to the details given herein. 

1. A lithium ion battery comprising: an anode comprising a substrate and at least one carbon nanotube array formed thereon, the carbon nanotube array comprising a plurality of carbon nanotubes, the carbon nanotubes being substantially parallel to each other and substantially perpendicular to the substrate; a cathode comprising a plurality of nanoparticles having a formula Li_(x)Co_(y)Ni_(z)O₂; an electrolyte; and a membrane separating the anode from the cathode.
 2. The lithium ion battery as described in claim 1, wherein an average diameter of the nanoparticles of Li_(x)Co_(y)Ni_(z)O₂ is in a range from 10 to 100 nanometers.
 3. The lithium ion battery as described in claim 1, wherein the carbon nanotubes comprise multi-walled carbon nanotubes.
 4. The lithium ion battery as described in claim 3, wherein an average diameter of an outermost wall of the multi-walled carbon nanotubes is in a range from 10 to 100 nanometers.
 5. The lithium ion battery as described in claim 3, wherein a pitch between any two adjacent multi-walled carbon nanotubes is in a range from 20 to 500 nanometers.
 6. The lithium ion battery as described in claim 3, wherein the multi-walled carbon nanotubes are formed by chemical vapor deposition.
 7. A lithium ion battery comprising: an anode comprising a substrate and a plurality of multi-walled carbon nanotubes formed thereon; a cathode comprising a plurality of nanoparticles having the formula Li_(x)Co_(y)Ni_(z)O₂; an electrolyte; and a membrane separating the anode from the cathode.
 8. The lithium ion battery as described in claim 7, wherein an average diameter of the nanoparticles of Li_(x)Co_(y)Ni_(z)O₂ is in a range from 10 to 100 nanometers.
 9. The lithium ion battery as described in claim 7, wherein the multi-walled carbon nanotubes are substantially parallel to each other and substantially perpendicular to the substrate
 10. The lithium ion battery as described in claim 9, wherein an average diameter of an outermost wall of the multi-walled carbon nanotubes is in a range from 10 to 100 nanometers.
 11. The lithium ion battery as described in claim 9, wherein a pitch between any two adjacent multi-walled carbon nanotubes is in a range from 20 to 500 nanometers.
 12. An anode assembly for a lithium ion battery, the anode comprising: a conductive substrate; and a plurality of multi-walled carbon nanotubes formed on the substrate, the multi-walled carbon nanotubes being substantially parallel to each other and substantially perpendicular to the substrate.
 13. The anode assembly for a lithium ion battery as described in claim 12, wherein an average diameter of an outermost wall of the multi-walled carbon nanotubes is in a range from 10 to 100 nanometers.
 14. The anode assembly for a lithium ion battery as described in claim 12, wherein a pitch between any two adjacent multi-walled carbon nanotubes is in a range from 20 to 500 nanometers.
 15. The anode assembly for a lithium ion battery as described in claim 12, wherein a plurality lithium ions are intercalated not only inside the multi-walled carbon nanotubes, but also in interstices between adjacent multi-walled carbon nanotubes.
 16. A cathode for a lithium ion battery, the cathode comprising: a conductive substrate; and a plurality of nanoparticles having the formula Li_(x)Co_(y)Ni_(z)O₂ formed on the substrate.
 17. The cathode for a lithium ion battery as described in claim 16, wherein an average diameter of the nanoparticles of Li_(x)Co_(y)Ni_(z)O₂ is in a range from 10 to 100 nanometers. 